WO2000066513A1 - Coke aciculaire destine a une electrode en graphite et procede de production associe - Google Patents

Coke aciculaire destine a une electrode en graphite et procede de production associe Download PDF

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Publication number
WO2000066513A1
WO2000066513A1 PCT/JP2000/002805 JP0002805W WO0066513A1 WO 2000066513 A1 WO2000066513 A1 WO 2000066513A1 JP 0002805 W JP0002805 W JP 0002805W WO 0066513 A1 WO0066513 A1 WO 0066513A1
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WO
WIPO (PCT)
Prior art keywords
coke
metal
sulfate
puffing
needle
Prior art date
Application number
PCT/JP2000/002805
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English (en)
Japanese (ja)
Inventor
Takayuki Kawarada
Yoichi Kawano
Original Assignee
Nippon Steel Chemical Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Steel Chemical Co., Ltd. filed Critical Nippon Steel Chemical Co., Ltd.
Publication of WO2000066513A1 publication Critical patent/WO2000066513A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
    • C04B35/532—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components containing a carbonisable binder

Definitions

  • the present invention relates to a needle coke for a graphite electrode and a method for producing the same, and more particularly, to a needle coke with less puffing in a graphitization step of electrode production and a method for producing the same.
  • Artificial graphite electrodes are produced by pulverizing coal-based coke or petroleum-based coke, adjusting it to a certain particle size distribution, kneading it with binder pitch, extruding, firing, impregnating, secondary firing, and graphitizing.
  • Graphitization is a process of heat treatment at about 300 ° C, and is generally performed using an LWG furnace (direct energization type).
  • LWG furnace direct energization type
  • puffing inhibitor As the puffing inhibitor, it is thought that puffing is caused by the desorption of sulfur at a temperature of 170 to 200 ° C, at which graphitization begins, so the sulfur is trapped and iron sulfide is trapped.
  • the desorption timing is shifted to the decomposition temperature of such compounds as iron oxide (Japanese Patent Application Laid-Open No. 55-110190) and nickels (Japanese Patent Application Laid-Open No. Japanese Patent Application Laid-Open No. 60-190491) and titanium oxide (Japanese Unexamined Patent Application Publication No. 2-51409) have been proposed and implemented.
  • These methods have different effects depending on the type of raw coke, such as the fact that coal-based coke has only a slight effect.
  • moisture or gas is generated from the inhibitor impregnated in coke, causing defects in the electrodes. There was a problem that the strength of the electrode was reduced.
  • a pitch from which quinoline-insoluble matter has been removed is used to remove nitrogen or sulfur content in the raw material pitch, which is a cause of puffing, using a hydrogenation catalyst.
  • a method of coking after hydrogenation is described below (JP-A-59-122585).
  • an object of the present invention is to reduce the profiling of a needle coke without increasing the cost of manufacturing a needle coat, and to improve the production yield and characteristics of a graphite electrode. And a method for producing the same. Disclosure of the invention
  • the present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, before kneading the metal compound used as the puffing inhibitor with the binder-pitch etc., directly adhere it to the coke surface in a solution state in advance and heat By processing, it overcomes the drawbacks of conventional inhibitors and finds that the effect of suppressing puffing increases, The present invention has been completed.
  • the twenty-first coke for a graphite electrode of the present invention contains, in the coke, one or more metal components or metals selected from magnesium, aluminum, titanium, konole, manganese, sodium, and nickel. It is characterized by containing 0.1 to 15% by weight of oxides and the like as ash content.
  • the coke before kneading with the binder pitch is reacted or decomposed by heat treatment with coke to produce a metal component or an oxide of the metal component, magnesium, aluminum,
  • a metal compound selected from titanium, cobalt, manganese, sodium, and nickel is directly adhered to the surface in a solution state, and after heat-treating at 300 to 150 ° C, one or more It is characterized in that it is attached to a 0.1 to 15 wt% core as a metal component or metal oxide.
  • the metal compound is at least one salt selected from the group consisting of magnesium sulfate, aluminum sulfate, titanium sulfate, covanolate sulfate, manganese sulfate, sodium chloride, sodium hydroxide, and Nigel sulfate.
  • the coke used for the production of the 21 dollar coke for the graphite electrode of the present invention is a raw coke produced by a delayed coking method using either one or both of a petroleum-based or coal-based heavy oil as a raw material.
  • the metal compound used in the present invention is a compound which reacts or decomposes by heating to produce one or more metal components or oxides (including complex oxides) of the metal components, etc. After adhering to the surface of the needle coat, heat treatment is performed at 300 to 150 ° C. Therefore, the metal compound that becomes a puffing inhibitor may be attached to the needle coat as an aqueous solution, or if it does not dissolve in water, it may be dissolved. The agent may be dissolved in a volatile liquid such as alcohol or benzene and then adhered to the coater.
  • Specific puffing inhibitors are selected from the group consisting of magnesium sulfate, aluminum sulfate, titanium sulfate, cobalt sulfate, manganese sulfate, sodium chloride, sodium hydroxide and sodium sulfate that are easily soluble in water. It is desirable to use at least one of them. What is important here is that these metal compounds are directly adhered to $ 21 coke and then heat-treated at 300 to 150 ° C in advance. The effect of the present invention is small even if it is added in the form of a metal oxide at the time of kneading, or if a compound that changes to a metal oxide by heating as described above is added.
  • the present invention after the compound which reacts or decomposes by heating to generate one or more metal components or an oxide of the metal component, etc., is directly adhered to the surface of the needle coke in the form of a solution, the content of 300 to 100 After heating at 500 ° C., binder pitch is kneaded with the raw material coke, and if necessary, a known puffing inhibitor such as iron oxide may be further added.
  • a known puffing inhibitor such as iron oxide may be further added.
  • the addition of iron oxide is preferable in that the effects of the present invention are further enhanced, as is clear from Examples and Comparative Examples described later.
  • the needle coke to which the metal compound is attached is subjected to heat treatment at 300 to 150 ° C. to remove water of crystallization of the attached compound and to remove the compound from one or more metal oxides.
  • heat treatment at 300 to 150 ° C. to remove water of crystallization of the attached compound and to remove the compound from one or more metal oxides.
  • Change to If the water of crystallization is not removed by heat treatment or if it is not converted into a metal oxide not only will the compound generate moisture during firing in the electrode manufacturing process, causing defects in the electrodes, but also the compound will decompose during firing, Gas is generated and the bulk density of the electrode decreases. For this reason, the strength of the electrode is insufficient, and the electrode may be damaged when used in an electric furnace.
  • the heat treatment temperature is lower than 300 ° C., water of crystallization of the compound is hard to be desorbed.
  • the temperature is preferably at least o ° C, more preferably at least 500 ° C so that the compound reacts with oxygen in the air or decomposes itself.
  • the temperature exceeds 150 ° C, graphitization of the $ 21 coat begins during the heat treatment of the compound, and it is difficult to effectively suppress puffing.
  • the amount of the metal compound adhering to the coke is 0.1 to 15% by weight, more preferably 0.5 to 3% by weight, as an ash content (metal component or metal oxide, etc.). . If the amount is outside the above range and the amount is insufficient, the effect of reducing the puffing is not practically sufficient, while if the amount is excessive, the effect of increasing the amount becomes insignificant, and the remaining ash content causes the electrode product to lose its effect. Has an unfavorable effect.
  • the needle coke for a graphite electrode thus obtained contains one or more metal components or metal oxides selected from magnesium, aluminum, titanium, manganese, cobalt, sodium and nickel in the coke, and an ash content of the coke. 0.1 to 15% by weight.
  • the ash content here is assumed to have been obtained by the ash measurement method described later.
  • the ash content of a conventional graphite electrode needle coater is suppressed to less than 0.1% by weight, but in the present invention, 0.1% by weight or more of a metal oxide or the like is contained as an ash content.
  • puff density graphitized bulk density (bulk density: BD) and ash used in the examples are shown below.
  • the heat-treated coke is reduced and then powdered to 60 mesh or less to obtain an average sample. Weigh at least about lg of sample into a pre-weighed magnetic dish. Keep the sample at 800 ° C in a matsufur furnace (furnace door slightly open so that it is in an oxidizing atmosphere) until the sample is completely incinerated. After complete incineration, cool in a desiccator and weigh the entire dish to calculate the ash content. In the same manner, the ash content of only coke without additive was also calculated, and the amount of metal oxides and the like attached to the coke was calculated from the difference between the former and the latter.
  • Example 2 The needle coke obtained by calcining the raw coke obtained in Example 1 was used. To a 3 kg of the calcined needle coke was added 700 g of a 3.4% by weight aqueous solution of aluminum sulfate (Example 2), and 7.50 g of a 3.5% by weight aqueous solution of nickel sulfate was added. (Example 3), 750 g of an aqueous solution of titanium sulfate having a concentration of 3.0% by weight was added (Example 4), left for 30 minutes, dried at 150 ° C., and then further dried at 90 ° C. Heat treatment was performed at 0 ° C. Table 1 shows the results of measuring the puffing and graphitized bulk density.
  • Examples 6 to 9 We used $ 21 coke obtained by calcining raw coke produced by delayed coking using coal-based heavy oil as a raw material. To 3 kg of the calcined $ 21 coke, 3.75 g of a 3.75 wt% aqueous solution of cobalt sulfate was added (Example 6), and 7.55 g of a 3.4 wt% aqueous solution of manganese sulfate were added.
  • Needle coke obtained by calcining raw coke produced by the delayed coking method using coal-based heavy oil as a raw material was used.
  • To 3 kg of the calcined needle coat was added 75 g of a 3.2% by weight aqueous copper sulfate solution, left for 30 minutes, dried at 150 ° C., and then further dried at 900 ° C. Heat treatment was performed at ° C.
  • Table 1 shows the results of measuring the puffing and graphitized bulk density.
  • the electrode was prepared without kneading iron oxide at the time of kneading the binder pitch.
  • Table 1 shows the results of measuring the puffing and graphitized bulk density.
  • the needle coke of the present invention which is obtained by adhering a compound that generates one or more metal oxides by heating to the surface of the needle coke and heat-treated at 300 to 150 ° C., is a graphite in the electrode manufacturing process. It can be used for the production of graphite electrodes that can effectively suppress puffing during the carbonization process, have a high bulk specific gravity (BD) after graphitization, have excellent strength characteristics, and sufficiently satisfy the required characteristics in production and quality. It can increase electrode yield, improve product characteristics, and provide significant industrial benefits.
  • BD bulk specific gravity

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Ceramic Products (AREA)
  • Coke Industry (AREA)

Abstract

L'invention concerne un coke aciculaire destiné à une électrode en graphite et caractérisé en ce qu'il contient un ou plusieurs composants métalliques choisis dans le groupe constitué par magnésium, aluminium, titane, cobalt, manganèse, sodium et nickel, ou un oxyde ou analogue d'un de ces métaux, en quantité comprise entre 0,1 et 15 % en poids, en tant que teneur en cendres. L'invention concerne également un procédé de production d'un coke aciculaire destiné à une électrode en graphite, ce procédé comprenant les étapes consistant à préparer une solution d'un composé d'un métal choisi dans le groupe constitué par magnésium, aluminium, titane, cobalt, manganèse, sodium et nickel, lequel composé peut former un composant métallique, un oxyde de composant métallique ou analogue, par chauffage avec un coke, de manière à adhérer directement sur la surface du coke avant mélange de celui-ci avec un brai de houille, et à soumettre le coke avec le composé à un traitement thermique, à une température comprise entre 300 et 1500 °C, de façon à produire un coke aciculaire sur la surface duquel adhèrent 0,1 à 15 % en poids d'un ou de plusieurs composants métalliques, oxydes métalliques ou analogue.
PCT/JP2000/002805 1999-04-30 2000-04-28 Coke aciculaire destine a une electrode en graphite et procede de production associe WO2000066513A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP11/124910 1999-04-30
JP12491099 1999-04-30
JP11192053A JP2001011471A (ja) 1999-04-30 1999-07-06 黒鉛電極用ニードルコークス及びその製造方法
JP11/192053 1999-07-06

Publications (1)

Publication Number Publication Date
WO2000066513A1 true WO2000066513A1 (fr) 2000-11-09

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5173555B2 (ja) * 2008-04-24 2013-04-03 Ｊｆｅケミカル株式会社 黒鉛質材料の製造方法、リチウムイオン二次電池用負極材料およびリチウムイオン二次電池
KR101568022B1 (ko) 2013-12-24 2015-11-11 주식회사 포스코 리튬 이차 전지용 인조흑연 음극재의 제조 방법 및 이로부터 제조된 리튬 이차 전지용 인조흑연 음극재
EP4321482A1 (fr) * 2021-04-09 2024-02-14 Mitsubishi Chemical Corporation Coke d'aiguille pour électrode de graphite, méthode de fabrication de coke d'aiguille et inhibiteur

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4140623A (en) * 1977-09-26 1979-02-20 Continental Oil Company Inhibition of coke puffing
JPS60190491A (ja) * 1984-03-13 1985-09-27 Nittetsu Kakoki Kk コ−ルタ−ルピツチコ−クス
JPS6110017A (ja) * 1984-06-23 1986-01-17 Nippon Steel Chem Co Ltd 黒鉛電極の製造方法
JPS63288964A (ja) * 1987-05-20 1988-11-25 Toyo Carbon Kk 炭素成形体の製造法
US4875979A (en) * 1988-03-07 1989-10-24 Union Carbide Corporation Treatment of petroleum cokes to inhibit coke puffing
JPH0251409A (ja) * 1988-08-16 1990-02-21 Mitsubishi Kasei Corp 炭素成形体用ニードルコークスの製造方法
JPH0251410A (ja) * 1988-08-16 1990-02-21 Mitsubishi Kasei Corp 炭素成形体用ニードルコークスの製造法
US5068026A (en) * 1989-03-06 1991-11-26 Sigri Gmbh Process for the production of non-puffing shaped carbon bodies
US5104518A (en) * 1989-03-06 1992-04-14 Sigri Gmbh Process for the inhibition of the puffing of cokes produced from coal tar pitches
WO1999037595A1 (fr) * 1998-01-26 1999-07-29 Nippon Steel Chemical Co., Ltd. Procede de preparation de coke aciculaire pour electrodes de graphite

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4140623A (en) * 1977-09-26 1979-02-20 Continental Oil Company Inhibition of coke puffing
JPS60190491A (ja) * 1984-03-13 1985-09-27 Nittetsu Kakoki Kk コ−ルタ−ルピツチコ−クス
JPS6110017A (ja) * 1984-06-23 1986-01-17 Nippon Steel Chem Co Ltd 黒鉛電極の製造方法
JPS63288964A (ja) * 1987-05-20 1988-11-25 Toyo Carbon Kk 炭素成形体の製造法
US4875979A (en) * 1988-03-07 1989-10-24 Union Carbide Corporation Treatment of petroleum cokes to inhibit coke puffing
JPH0251409A (ja) * 1988-08-16 1990-02-21 Mitsubishi Kasei Corp 炭素成形体用ニードルコークスの製造方法
JPH0251410A (ja) * 1988-08-16 1990-02-21 Mitsubishi Kasei Corp 炭素成形体用ニードルコークスの製造法
US5068026A (en) * 1989-03-06 1991-11-26 Sigri Gmbh Process for the production of non-puffing shaped carbon bodies
US5104518A (en) * 1989-03-06 1992-04-14 Sigri Gmbh Process for the inhibition of the puffing of cokes produced from coal tar pitches
WO1999037595A1 (fr) * 1998-01-26 1999-07-29 Nippon Steel Chemical Co., Ltd. Procede de preparation de coke aciculaire pour electrodes de graphite

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